Novel compositions of material, especially lubricants and pressure transmitting means, the production and use thereof

ABSTRACT

The invention relates to novel compositions of matter which may advantageously be used as lubricants or pressure transfer media or else for functional liquids and lubricant additives. The lubricants according to the invention are the reaction products of an electro-philic addition of linear or branched, aliphatic or aromatic carboxylic acids, carboxylic anhydrides, carbonyl halides or novel neoacids to the double bonds of fatty acids, esters thereof and/or of other fatty acid derivatives and also of synthetic esters. Owing to their increased oxidation resistance compared to the starting materials and also their low toxicity, the novel class of synthetic esters based on oleochemicals may find use in novel environmentally compatible lubricants, pressure transfer systems, functional liquids and lubricant additives.

[0001] The present invention relates to compositions of matter which aresuitable as lubricants and pressure transfer media comprising esters offatty acids, of fatty acid derivatives and of mixtures thereof, and alsoto a process for preparing these esters according to the invention byadding carboxylic acids and/or carboxylic anhydrides and/or carbonylhalides to the double bond and/or double bonds of fatty acids, fattyacid derivatives or mixtures thereof, and also to the use of theseesters according to the invention as environmentally compatible, easilybiodegradable lubricants, lubricant components, lubricant additives,hydraulic oils, pressure transfer media, transmission oils andfunctional liquids.

PRIOR ART

[0002] In Germany alone, 520,000 t of lubricant per year pass into theenvironment via leakage in seals or pipes, during repairs, in oilaccidents or by vaporization and atomization. The use of renewable rawmaterials, directly or in the form of their conversion products, notonly saves fossil raw materials, but also equalizes the CO₂ balance andalso avoids set-aside to reduce farming overproduction.

[0003] The limits of application for natural oils and the fatty acidsderived from them result from their low stability toward thermal andoxidative loading and hydrolysis and also from the limited cold flowbehavior, i.e. properties which can only gradually be influenced byadding chemical additives such as sulfonates, phenol derivatives oramines. Breeding measures to enrich certain fatty acids in thetriglycerides of plant oils may lead to improvement in the technicalproperties. However, chemical conversions which can attack both thealcohol components and the acid components are more important.

[0004] The attack point for the oxidative aging of natural oils and thefatty acids derived from them are the double bonds contained therein,and the double bonds having (Z) conformation are especially easilyattacked by oxygen to form peroxidic intermediates.

[0005] The oxidation stability of natural oils or of the fatty acidsderived from them may be increased, for example, by partialhydrogenation of the polyunsaturated acids.

[0006] The addition of formic or acetic acid to methyl oleate andsubsequent hydrolysis of the ester obtained is known [H. B. Knight, R.E. Koos, D. Swern, J. Am. Chem. Soc., 1953, 75, 6212; H. B. Knight, R.E. Koos, D. Swern, J. Am. Oil Chem. Soc., 1954, 31, 1]. Boilinganhydrous formic acid adds to oleic acid without catalysis to 80%conversion in 24 hours. If small quantities of perchloric acid areadded, the reaction time is shortened to 5 minutes. Acetic acid adds tooleic acid without catalysis only to a negligible extent; catalysis byperchloric acid leads to 40% conversion in 15 minutes, and a threefoldexcess of acetic acid gives conversions of from 60 to 70% after 70 hours[W. O. Munns, S. Kairys, D. A. Manion, J. Am. Oil Chem. Soc., 1963, 40,22].

[0007] The aim of all the processes described is not the preparation ofthe formyloxy or acetoxy compounds, but instead the hydrolysis thereofto give monohydroxystearic acid, which is an important component inpreparing lubricant fats and oils and also plasticizers.

[0008] The acetoxylation to obtain the monoesters which are ofindustrial interest as plasticizers of PVC has been investigated undercatalysis with the acid ion exchanger Amberlyst 15 [L. T. Black, R. E.Beal, J. Am. Oil Chem. Soc., 1967, 44, 310]. At a methyl oleate/catalystmass ratio of two and a 50-fold molar excess of acetic acid, 42% yieldsof methyl acetoxystearate were obtained over a period of 8 hours. Whenformic acid was used, no catalytic effect of Amberlyst 15 could bedetected. The addition of propionic and butyric acid was likewiseinvestigated, but these acids gave lower yields than acetic acid. Nobranched carboxylic acids were used. However, no systematicinvestigation of the rheological properties of the adducts obtained wascarried out. The regeneration of the catalyst is not described in theliterature. The aim of these experiments was an alternative route ofpreparing methyl monohydroxystearates, which are obtained by hydrolysisof the methyl acetoxy- and formyloxystearate intermediates.

[0009] None of the acyloxylations of fatty acids or fatty acidderivatives known from the literature mentions or makes known the use ofreaction products as lubricants and/or pressure transfer media.

[0010] The described processes based on fatty acids, natural fatty acidderivatives and mixtures thereof provide novel materials for lubricantswhich surprisingly improve the critical properties of these naturalcrude products such as low aging stability, low oxidation stability, lowhydrolysis stability and critical cold properties, without adverselyaffecting their advantages such as good lubricity or low viscositydependence on temperature. The flexibility of the reaction allowscertain properties such as viscosity, cold properties and elastomercompatibility to be set to specific values within wide ranges.

[0011] According to the invention, novel lubricants and pressuretransfer media based on fatty acids and/or fatty acid derivatives havebeen found which are acyloxylated at at least one double bond,preferably by unbranched or branched carboxylic esters, in particularthose of the general chemical formula I:

[0012] where R₁₄ is a carboxylic acid radical R—COOH where R is analkyl, alkenyl, dienyl or polyenyl radical having from 2 to 20 carbonatoms and from 0 to 4 double bonds, preferably having from 3 to 11carbon atoms and from 0 to 2 double bonds, for example, n-carboxyheptyl,n-carboxyundecyl, n-carboxy-4-heptenyl or esters thereof withmonoalcohols, diols or polyols, such as methanol, ethanol, glycerol,pentaerythritol or trimethylolpropane;

[0013] where R₁₅ is an alkyl, alkenyl, dienyl or polyenyl radical havingfrom 2 to 20 carbon atoms and from 0 to 4 double bonds, preferably from3 to 14 carbon atoms and from 0 to 3 double bonds, in particular from 3to 10 carbon atoms and from 0 to 2 double bonds, for example, n-hexyl,n-octyl, 2-octenyl or 2,5-octadienyl;

[0014] and where R₁₆ is H or R₁₆ is

[0015] an alkyl radical having from 1 to 10 carbon atoms, for example

[0016] methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,pentyl, hexyl, octyl, decyl or cyclohexyl;

[0017] an aryl radical having alkyl and other substituents on thearomatic ring, for example

[0018] phenyl, methylphenyl, ethylphenyl, mesityl, cumyl,p-nitrophenylxylyl, hydroxyphenyl or naphthyl;

[0019] an aralkyl radical, for example

[0020] benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, cumylmethylor mesitylmethyl;

[0021] an alkyloxy radical having from 1 to 10 carbon atoms andphosphorus or sulfur as a further heteroatom, for example

[0022] methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy,3-thiabutyloxy, 3-phosphabutyloxy;

[0023] an aralkyloxy radical having alkyl and heteroatom-containingsubstituents on the aromatic ring, for example

[0024] benzyloxy, 1-phenylethyloxy, (2-methyl)phenylmethoxy,p-sulfobenzyloxy or p-nitrobenzyloxy;

[0025] and where R₁₇=R₁₈=R₁₆, except when R₁₆ is H,

[0026] where R₁₆, R₁₇ and R₁₈ may be identical or different and, whenR₁₆ is H, R₁₇ and R₁₈ may be identical or different.

[0027] For the purposes of the present invention, acyloxylation refersto the introduction of an acyloxy radical of the formula —O—CO—R into anorganic compound, as described, for example, by Römpp, 9th edition,1995, page 47, preferably by addition of a carboxylic acid or acarboxylic acid derivative to the double bond of a fatty acid or fattyacid derivative.

[0028] Compounds of the general formula I may be prepared usingcompounds of the general formula II as double bond components

[0029] where R₁₄ is a carboxylic acid radical R—COOH where R is analkyl, alkenyl, dienyl or polyenyl radical having from 2 to 20 carbonatoms and from 0 to 4 double bonds, preferably having from 3 to 11carbon atoms and from 0 to 2 double bonds, for example, n-carboxyheptyl,n-carboxyundecyl, n-carboxy-4-heptenyl or esters thereof withmonoalcohols, diols or polyols, such as methanol, ethanol, glycerol,pentaerythritol or trimethylolpropane;

[0030] and where R₁₅ is an alkyl, alkenyl, dienyl or polyenyl radicalhaving from 2 to 20 carbon atoms and from 0 to 4 double bonds,preferably from 3 to 14 carbon atoms and from 0 to 3 double bonds, inparticular from 3 to 10 carbon atoms and from 0 to 2 double bonds, forexample, n-hexyl, n-octyl, 2-octenyl or 2,5-octadienyl.

[0031] Such double bond components may be represented by oleic acid,linoleic acid, linolenic acid, palmitoleic acid, eicosenoic acid anderucic acid and mixtures thereof, and by methyl oleate, methyllinoleate, methyl linolenate and methyl palmitoleate.

[0032] The double bond components used may also be glycerol trioleate,glycerol trilinolate, glycerol trilinoleate, trimethylolpropanetrioleate, trimethylolpropane trilinolate, trimethylolpropanetrilinoleate, pentaerythritol tetraoleate, pentaerythritoltetralinolate, pentaerythritol tetralinoleate or mixtures thereof orrenewable raw materials such as rapeseed oil, sunflower oil, palm oil,coconut oil or olive oil.

[0033] The double bond components used may also be poly-unsaturatedfatty acids and/or fatty acid derivatives where a portion of the doublebonds has first been hydrogenated and carboxylic acids and/or carbonylhalides and/or carboxylic anhydrides have then been added to theremaining double bonds.

[0034] To prepare the novel lubricants and pressure transfer mediaaccording to the invention, at least one double bond of the fatty acidsand/or fatty acid derivatives and mixtures thereof should beacyloxylated using unbranched carboxylic acids of the formula IV,

[0035] where R₈ is H or a linear alkyl radical having from 2 to 16carbon atoms, preferably from 2 to 4 carbon atoms, or an aromaticradical whose aromatic core may be substituted by alkyl groups and/orhalogens such as F.

[0036] Other added carboxylic acids fall under the general formula III

[0037] where R₁₆ is H or R₁₆ is

[0038] an alkyl radical having from 1 to 10 carbon atoms, for example

[0039] methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,pentyl, hexyl, octyl, decyl or cyclohexyl;

[0040] an alkenyl radical having from 1 to 10 carbon atoms, for example

[0041] ethenyl, n-propenyl, isopropenyl, hexenyl, 3-methylpentenyl or3-ethylbutenyl;

[0042] an aryl radical having alkyl and other substituents on thearomatic ring, for example

[0043] phenyl, methylphenyl, ethylphenyl, mesityl, cumyl,p-nitrophenylxylyl, hydroxyphenyl or naphthyl;

[0044] an aralkyl radical, for example

[0045] benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, cumylmethylor mesitylmethyl;

[0046] an alkyloxy radical having from 1 to 10 carbon atoms andphosphorus or sulfur as a further heteroatom, for example

[0047] methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy,3-thiabutyloxy, 3-phosphabutyloxy;

[0048] an aralkyloxy radical having alkyl and heteroatom-containingsubstituents on the aromatic ring, for example

[0049] benzyloxy, 1-phenylmethyloxy, (2-methyl)phenylmethoxy,p-sulfobenzyloxy or p-nitrobenzyloxy;

[0050] and where R₁₇=R₁₈=R₁₆, except when R₁₆ is H,

[0051] where R₁₆, R₁₇ and R₁₈ may be identical or different and, whenR₁₆ is H, R₁₇ and R₁₈ may be identical or different.

[0052] Particular preference is given to adding neocarboxylic acids ofthe general formula V

[0053] where R₉, R₁₀, R₁₂ and/or R₁₃ are identical or different and arehydrogen, straight-chain or branched alkyl, alkenyl or alkynyl radicalshaving up to 18 carbon atoms, cycloalkyl or cycloalkenyl radicals havingfrom 5 to 8 carbon atoms, aryl, aralkyl or alkenylaryl radicals havingfrom 6 to 16 carbon atoms or heterocyclic radicals, where each of the R₉and R₁₀ and/or R₁₂ and R₁₃ radical pairs together with the carbon atomto which they are bonded may form a cycloalkane, cycloalkene or aheterocycle having from 5 to 7 ring members, and R₉, R₁₀, R₁₂ and R₁₃may additionally carry substituents, in particular those which are inertunder the reaction conditions, and R₁₁ is hydrogen or a straight-chainor branched alkyl radical.

[0054] Preference is given to carboxylic acids where R₉, R₁₀, R₁₂ andR₁₃ are identical or different and are hydrogen, straight-chain orbranched alkyl radicals having from 1 to 12, in particular from 1 to 6carbon atoms, alkenyl or alkynyl radicals having from 2 to 12, inparticular from 2 to 6 carbon atoms. Preference is further given tocompounds R₉, R₁₀, R₁₂ and R₁₃ are cycloalkyl or cycloalkenyl radicalshaving 5 or 6 carbon atoms, or are aryl, alkylaryl, aralkyl oralkenylaryl radicals having from 6 to 12 carbon atoms or areheterocyclic radicals which contain one or more nitrogen and/or oxygenand/or sulfur atoms. Furthermore, neocarboxylic acids are preferredwhere R₁₁ is hydrogen or a straight-chain or branched alkyl radicalhaving from 1 to 12, in particular from 1 to 8, preferably from 1 to 4carbon atoms. R₁₁ is particularly preferably hydrogen.

[0055] Examples of alkyl, alkenyl and alkynyl radicals include themethyl, ethyl, n-propyl, isopropyl, propenyl, isopropenyl, n-butyl,isobutyl, n-butenyl, i-butenyl, n-butynyl, pentyl, pentenyl, pentynyl,hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl,decenyl, dodecyl and dodecenyl radicals.

[0056] Representative examples of cycloalkyl radicals includecyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl and cyclohexenylradicals.

[0057] Examples of useful aromatic radicals include the phenyl, benzyl,2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylbutyl,3-phenylbutyl and 4-phenylbutyl radicals.

[0058] Examples of heterocyclic radicals include furan, dihydrofuran,tetrahydrofuran, thiophene, dihydrothiophene, pyridine and thiopyranradicals.

[0059] The alkyl, cycloalkyl, aromatic and heterocyclic radicals may besubstituted, in particular by radicals which are inert under thereaction conditions, such as halogen, alkoxy, carboxyl or carboxylategroups. However, it is not ruled out that in individual casessubstituents are deliberately chosen which are changed in the course ofthe reaction, for example, formyl groups which are converted to formoxyradicals.

[0060] According to the invention, for example, the following novelcarboxylic acids branched in the alpha-position to the carboxyl groupmay be used in this manner such as:

3-Propyloxy-2,2-dimethylpropionic acid

[0061]

[0062] The spectroscopic data of this compound were determined asreported below. ¹H-NMR 0.89 ppm tr 3H, 1.19 ppm 2 6H, 3.42 ppm s 2H,3.40 ppm s 2H, 1.56 ppm m 2H ¹³C-NMR 10.66 ppm CH₃, 23.06 ppm CH₂, 77.54and 73.69 ppm O—CH₂, 43.83 ppm quaternary C, 22.46 ppm 2 CH₃, 183.01 ppmC═O IR 1706 cm⁻¹ C═O, 2976, 2935, 2879 cm⁻¹ v_(s.as) CH₂, CH₃, broadshoulder at 2700-2500 cm⁻¹ MS m/z: 175 (M⁺.), 131, 115, 101, 102, 87, 83

3-Butyloxy-2,2-dimethylpropionic acid

[0063]

[0064] The following spectroscopic data were determined: ¹H-NMR 0.90 ppmtr 3H, 1.34 ppm m 2H, 1.53 ppm q 2H, 3.45 ppm tr 2H, 3.42 ppm s 2H, 1.19ppm s 6H ¹³C-NMR 14.01 ppm CH₃, 19.69 ppm CH₂, 31.95 ppm CH₂, 77.65 and71.80 ppm O—CH₂, 43.87 ppm quaternary C, 22.44 ppm 2 CH₃, 183.72 ppm C═OIR 1706 cm⁻¹ C═O, 2971, 2935, 2879 cm⁻¹ v_(s.as) CH₂, CH₃ broad shoulderat 2700-2500 cm⁻¹ MS m/z 189 (M⁺.), 131, 114, 102, 101, 87, 73

3-Isobutoxy-2,2-dimethylpropionic acid

[0065]

[0066] The following spectroscopic data were determined for thiscompound: ¹H-NMR 0.88 ppm s 3H, 0.89 ppm s 3H, 1.84 ppm m 1H, 3.20 ppm d2H, 3.41 ppm s 2H, 1.20 ppm 2 6H ¹³C-NMR 19.36 ppm 2 CH₃, 28.70 ppm CH,78.83 and 77.75 ppm O—CH₂, 22.44 ppm 2 CH₃, 43.87 ppm quaternary C,183.04 ppm C═O IR 1706 cm⁻¹ C═O, 2976, 2935, 2868 cm⁻¹ v_(s.as) CH₂,CH₃, broad shoulder at 2700-2500 cm⁻¹ MS m/z: 189 (M⁺.), 131, 115, 102,101, 87, 73

3-(2-Ethylbutyloxy)-2,2-dimethylpropionic acid

[0067]

[0068] For this compound, the following spectroscopic data weremeasured: ¹H-NMR 0.93 ppm tr 3H, 0.86 ppm tr 3H, 1.59 ppm m 4H, 2.22 ppmm 1H, 3.33 ppm d 2H, 3.40 ppm s 2H, 1.19 ppm s 6H ¹³C-NNR 11.87 and11.26 ppm CH₃, 23.86 and 25.16 ppm CH₂, 49.34 ppm CH, 77.92 and 74.36ppm O—CH₂, 22.46 ppm 2 CH₃, 43.90 ppm quaternary C, 183.16 ppm C═O IR1706 cm⁻¹ C═O, 2966, 2935, 2879 cm⁻¹ v_(s.as) CH₂, CH₃ broad shoulder at2700-2500 cm⁻¹ MS m/z: 217 (M⁺.), 185, 145, 133, 131, 115, 102, 101, 85,73

3-Benzyloxy-2,2-dimethylpropionic acid

[0069]

[0070] The compound has the following spectroscopic data: ¹H-NNR 7.20ppm m 5H, 4.37 ppm s 2H, 3.35 ppm s 2H, 1.08 ppm s 6H ¹³C-NMR 125-130ppm aromatic C, 77.13 and 73.28 ppm O—CH₂, 21.87 ppm 2 CH₃, 43.80 ppmquaternary C, 182.89 ppm C═O IR 1701 cm⁻¹ C═O, 3094, 3063, 3033 cm⁻¹v_(ar) CH, 2984, 2909, 2878 cm⁻¹ v_(s.as) CH₂, CH₃, broad shoulder at2700-2500 cm⁻¹ MS m/z: 222 (M⁺.), 191, 116, 107, 101, 91, 65

3-(2-Methylphenyloxy)-2,2-dimethylpropionic acid

[0071]

[0072] The compound gave the following spectroscopic data: ¹H-NMR7.0-7.3 ppm m 4H, 2.28 ppm s 3H, 3.48 ppm s 2H, 3.44 ppm s 2H, 1.21 ppms 6H ¹³C-NMR 125-130 ppm aromatic C, 77.31 and 72.28 ppm O—CH₂, 43.78ppm quaternary C, 22.46 ppm CH₃— ar, 18.82 and 15.32 ppm CH₃, 182.79 ppmC═O IR 1703 cm⁻¹ C═O, 3073, 3027 cm⁻¹ v_(ar) CH, 2976, 2935, 2868 cm⁻¹v_(s.as) CH₂, CH₃, broad shoulder at 2700-2500 cm⁻¹ MS m/z: 237 (M⁺.),209, 193, 145, 131, 121, 115, 105

[0073] The carboxylic acids mentioned above are obtained by catalyticgas phase isomerization of appropriately substituted 1,3-dioxanes togive aldehydes and the subsequent oxidation thereof to the carboxylicacids. The conversion of 1,3-dioxanes to aldehydes is described inEP-A-0 199 210.

[0074] The isomerization catalysts used are acidic solids. These includemetal oxides such as Al₂O₃, TiO₂, SiO₂, ZrO₂, Nb₂O₅ or phosphates suchas boron phosphate, aluminum phosphate or iron phosphate or sulfatedzirconium dioxide or titanium dioxide, but also ion exchange resins suchas Amberlyst, Nafion and Nafion/silica composites.

[0075] Catalysts used for the oxidation of the aldehydes obtained byisomerization of the dioxanes are advantageously metals or transitiongroups I and VIII of the Periodic Table in metallic form or in the formof their oxides. These catalysts may be used pure or supported.Preference is given to using silver, which is used on supports, orsilver(I) oxide, which is used in pure form.

[0076] To prepare the novel lubricants and pressure transfer mediaaccording to the invention, the double bonds of the natural fatty acids,natural fatty acid derivatives and mixtures thereof may be acyloxylatednot with carboxylic acids, but instead with the corresponding carboxylicanhydrides and/or carbonyl halides. The fatty acids or fatty acidderivatives used may be of natural or synthetic origin. In the case ofcertain carboxylic acid component, the use of further solvents in theacyloxylation may be unnecessary, and instead the carboxylic acidcomponent itself may be used as solvent in a molar excess in the rangefrom 1.2 to 150 mol %.

[0077] The reactions are carried out in the presence of homogeneous orheterogeneous catalysts. It was shown that the use of homogeneous orheterogeneous acid catalysts gives good conversions and highselectivities in the addition reaction.

[0078] According to the invention, heterogeneous catalysts such aszeolites, solid phosphoric acid, phosphates of aluminum, boron, iron,strontium, cerium and zirconium, oxides such as Al₂O₃, SiO₂, B₂O₃,Fe₂O₃, ZrO₂, SnO₂ and GeO₂ and organic ion exchangers such as Amberlystor Nafion, which are easily removed from the products formed, areparticularly advantageous. The use of zeolites as heterogeneouscatalysts is known [H. Kessler, Comprehensive Supramolecular ChemistryVolume 7: Solid-state Supramolecular Chemistry: Two- andThree-dimensional inorganic Network 1996, pp. 425-464; L. B. McCusker,Comprehensive Supramolecular Chemistry Volume 7: Solid-stateSupramolecular Chemistry: Two-and Three-dimensional Inorganic Network1996, pp. 393-424], and likewise the use of aluminum phosphates [E. M.Flanigen, B. M. Lok, R. L. Patton, S. T. Wilson in Y. Murakami, A. Ijimaand J. W. Ward (Eds.), New Developments in Zeolite Science andTechnology, Proc. 7^(th) Intl Zeolite Conf., Tokyo, 1986, Kodansha Ltd.Tokyo and Elsevier, Amsterdam, pp. 101-112]. Nafion/silica compositematerials in particular deliver good results. In this case, it isadvantageous to dry the catalyst before use in the reaction for morethan one hour at elevated temperature under reduced pressure. Theheterogeneous catalysts mentioned are easy to regenerate and mayaccordingly be used repeatedly in the process which is particularlyadvantageous from a technical point of view. While formic acid also addsto the double bond of natural fatty acids and fatty acid derivativeswithout catalyst, the use of higher carboxylic acids in the absence ofcatalysts gives no or only very low conversion, although the reactionwith carboxylic acids may in individual cases also proceedautocatalytically.

[0079] Useful homogeneous acid catalysts include, inter alia, H₂SO₄,methylsulfonic acid, H₃PO₄ and derivatives thereof, H₃BO₃, HNO₃, HCl,HF, HFBF₃, AlCl₃, FeCl₃, SnCl₂, AlBr₃ and FeBr₃.

[0080] According to the invention, novel esters of natural fatty acidsand fatty acid derivatives may be prepared according to the followingequation 1 or equation 2:

[0081] The analysis was carried out by HPLC (high pressure liquidchromatography) and GC (gas chromatography). Additional information onthe identity of the products prepared was obtained by mass spectrometry(MS). The addition products formed may be separated from their startingproducts by distillation or column chromatography and isolated in apurity in the range from 70 to 99% and then characterized by NMR and IRspectroscopy.

[0082] For example, the ester having the following chemical formula(compound III) has the following characteristic features: Compound III

¹H-NMR 0.8 ppm tr 3H (chain end methyl group), 1.13 ppm s 9H (tert-butylgroup), 1.19-1.6 ppm a plurality of broad peaks (methylene groups of thechain), 2.12 ppm tr 2H (CH₂ group next to the methyl ester group), 3.59ppm s 3H (O—CH₃ group) and 4.78 ppm q 1H (ester-substituted CH group)¹³C-NMR 14.12 ppm (chain end CH₃ group), 27.25 ppm (tert-butyl group), 7peaks of 22.66-34.14 ppm (methylene groups of the chain), 38.84 ppm[(CH₃)₃C], 51.44 ppm (O—CH₃ group), 73.81 ppm (ester-substituted CHgroup), 174.35 ppm (—CH₂CO₂CH₃), 178.27 ppm ((CH₃)₃C—CO₂—CH) IR 1164cm⁻¹ V_(as) C—O—C, 1283 cm⁻¹ V_(as) C—O—C, 1435 cm⁻¹ δs CH₂/—CH₂—CO—C,1462 cm⁻¹ δas CH₃, 1480 cm⁻¹ δs CH₂, 1742, 1726 cm⁻¹ C═O, 2950, 2926,2856 cm⁻¹ v_(s.as) CH₂, CH₃ MS m/z: 399 (M⁺.), 313, 297, 265, 247, 220,111, 97, 95, 83, 69, 57, 55

[0083] Boiling point: 170-174° C./1-10⁻¹ mbar Elemental analysis:C_(found): 72.4% C_(calculated): 72.3% H_(found): 12.0% H_(calculated):11.6%

[0084] According to the invention, it is advantageous for esterformation to use the carboxylic acid and/or the carboxylic anhydrideand/or the carbonyl halides in excess and as the solvent to avoid theuse of additional solvents.

[0085] The carboxylic acid is added to the double bonds of theoleochemical component. The carbenium ion mechanism may lead to a smallextent to double bond isomerization. Reaction by-products may includepolymers and to a small extent transesterification products by cleavageof the fatty acid ester and esterification of the carboxylic acidcomponent present in excess.

[0086] After the end of the reaction, the heterogeneous catalysts can beeasily filtered off, washed and regenerated to restore the startingactivity.

[0087] Unreacted carboxylic acids or derivatives thereof, like the oilcomponent, may be distillatively or chromatographically removed from theproduct formed. Likewise, the addition products formed may be isolatedby distillation or column chromatography in a purity of from 70 to 99%and characterized spectroscopically by NMR and IR.

[0088] The carboxylic acid or derivatives thereof are added to thenatural fatty acids and natural fatty acid derivatives in the liquidphase and at temperatures in the range from 0 to 400° C., preferablyfrom 25 to 250° C., in particular from 70 to 180° C. The reaction iscarried out at pressures in the range from 1000 to 10,000 hPa,preferably from 1000 to 5000 hPa, in particular from 1000 to 2000 hPa.Catalyst space velocities of from 0.001 mmol to 50 mol of reactant pergram of catalyst are used, preferably from 0.01 mmol to 30 mol, inparticular from 0.1 to 10 mol.

[0089] The reaction time is in the range from one minute to 12 days,preferably in the range from 10 minutes to 5 days, in particular fromone hour to 48 hours. The molar excess of the acid component compared tothe oil component is from 0.3 to 300, preferably from 1.2 to 150, inparticular from 10 to 80.

[0090] Higher branching of the carboxylic acid or carboxylic acidderivative added normally reduces their reactivity. However, theselectivity of the reaction is at the same time distinctly increased,since the lower acid strength results in fewer side reactions such aspolymerization and transesterification. When the reaction is scaled up,the good selectivities and conversions can be retained, but longerreaction times are sometimes required.

[0091] The reaction may be carried out in a batchwise or continuousprocess. Thus a batchwise process at atmospheric pressure may employstirred tank reactors; when working under pressure, stainless steelautoclaves may be used. In the semicontinuous method, stirred tankbatteries are used. In the continuous reaction procedure, preference isgiven to using tubular reactors with fixed catalyst beds. Loop andfluidized bed reactors may also be used.

[0092] To carry out the reaction, the acid component is added to thenatural fatty acids or natural fatty acid derivatives used as thereactant in the presence of the catalyst at ambient temperature withstirring and the flask is introduced into a heating bath of the desiredreaction temperature. The reaction is effected by means of stirring andcooling by means of a reflux condenser. Analysis is effected bywithdrawing a defined sample quantity at different time intervals andanalyzing it by means of HPLC or GC. After the end of the reaction, thecatalyst is filtered off, washed with an organic solvent and regeneratedusing hydrochloric or nitric acid. Regeneration may also be effectedunder an oxygen atmosphere by burning off carbon deposits (zeolites).The reaction mixture is fractionated by high vacuum distillation orcolumn chromatography and remaining oil and acid components are recycledinto the reaction.

[0093] The oil component used may be modified by preceding partialhydrogenation.

[0094] To this end, the natural fatty acids or natural fatty acidderivatives may be reacted under elevated pressure with hydrogen overvarious heterogeneous catalysts, for example, nickel, platinum orpalladium on support materials, at temperatures of around 150° C. in theliquid phase. Carboxylic acids can be catalytically added to theremaining double bonds according to the above description.

[0095] The novel lubricants and pressure transfer media according to theinvention have high oxidation and hydrolysis stability, improvedviscosity properties with a wide viscosity range, low vapor pressure andoptimized lubricant film formation and also reduced frictional moments,for example in a spindle bearing. They have good biodegradability. Thesubstances or substance mixtures according to the invention may alsofind use as functional liquids and lubricant additives.

[0096] The invention will now be more particularly described withreference to illustrative examples.

EXAMPLES

[0097] Catalyst A:

[0098] Catalyst A=®Nafion SAC 13, i.e. Nafion/silica composite materialhaving a Nafion content of 13%. Nafion is a registered trademark ofDuPont. It is a perfluorinated polymer which is obtained by sulfonationof super acid functions. Coprecipitation of Nafion with silica gel givesmaterials having varying Nafion contents and a surface area of from 300to 400 m²/g, which are referred to as Nafion composites.

[0099] Catalyst B:

[0100] Catalyst B=®Amberlyst 15 from Fluka having a surface area of 45m²/g and a porosity of 32%. Amberlyst is a trademark of Rohm and HaasCompany. Macroreticular ion exchangers are prepared by copolymerizationof styrene with from 3 to 5% of divinylbenzene for crosslinking. Theacid function is formed by SO₃H groups.

Examples 1 and 2 Formic Acid without Catalyst

[0101] 190 g of methyl oleate were reacted with 600 g of formic acidwith stirring using a magnetic stirrer bar at a temperature of 120° C.Stirring was effected for 18 h under reflux. After the reaction, asample was taken and analyzed by gas chromatography using a 60 mChrompack SE-54 column.

[0102] The reaction proceeded according to the following equation (3):

[0103] R_(A): H₃C—(CH₂)₆—CH₂— R_(B): —(CH₂)₇CO₂CH₃ Reaction time Molar CS Y Example [h] ratio: * [%] [%] [%] 1 18 20 72.5 96.5 70.0 2 18 26 85.591.1 77.9

[0104] The reaction mixture was fractionated under high vacuum. Formicacid came over at 54° C./150 torr, methyl oleate and remaining reactantcomponents at 133° C./1·10⁻¹ mbar and methyl 9(10)-formyloxystearate at160-174° C./1·10⁻¹ mbar. 105 g of product mixture having a methyl9(10)-formyloxystearate content of 90% were obtained.

[0105] Characterization of compound I=methyl 9(10)-formyloxystearate:¹H-NMR 0.83 ppm tr 3H (chain end methyl group), 1.19- 1.6 ppm aplurality of broad peaks (chain methylene groups), 2.25 ppm tr 2H (CH₂group next to the methyl ester group), 3.61 ppm s 3H (O—CH₃ group), 4.78ppm q 1H (ester- substituted CH group), 8.04 ppm s 1H (formyloxy group)¹³C-NMR 14.13 ppm (chain end CH₃ group), 7 peaks of 22.70-34.09 ppm(methylene groups of the chain), 51.44 ppm (O—CH₃ group), 74.53 ppm(ester-substituted CH group), 161.14 ppm (HCO₂OH), 174.31 ppm(—CH₂—CO₂—CH₃) IR 1183 cm⁻¹ v_(as) C—O—C (strong peak for formates),1377 cm⁻¹ δs CH₃, 1437 cm⁻¹ δs CH₂/—CH₂—CO—C, 1465 cm⁻¹ δas CH₃, 1377cm⁻¹ δs CH₂, 1742, 1725 cm⁻¹ C═O, 2928, 2856 cm⁻¹ v_(s.as) CH₂, CH₃ MSm/z: 343 (M⁺.), 313, 297, 265, 264, 246, 235, 222, 111, 109, 81, 67, 55

[0106] Boiling point: 160-174° C./1·10⁻¹ mbar Elemental analysis:C_(found): 70.4% C_(calculated): 70.13% H_(found): 11.38%H_(calculated): 11.18%

Example 3 Formic Acid with Amberlyst as Catalyst

[0107] Methyl oleate:  2.5 g Formic acid: 19.55 g Catalyst:  2.5 gTemperature: 120° C. Reaction C S Y Example Catalyst time [h] [%] [%][%] 3 Amberlyst 15 8 99.9 80.8 80.8

Example 4 Formic Acid with Nafion/Silica Composite SAC 13 as Catalyst

[0108] Reaction C S Y Example Catalyst time [h] [%] [%] [%] 4 Nafion SAC13 8 83.0 77.3 64.1

Example 5 Acetic Acid with Sulfuric Acid as Catalyst

[0109] Methyl oleate:  2.5 g Acetic acid: 25.5 g Catalyst:  2.5 gTemperature: 120° C. Reaction C S Y Example Catalyst time [h] [%] [%][%] 5 H₂SO₄ 20 90.1 40.5 36.5

Example 6 Acetic Acid with Phosphoric Acid on Silica as Catalyst

[0110] Reaction C S Y Example Catalyst time [h] [%] [%] [%] 6 H₃PO₄ onSiO₂ 24 80.4 51.4 41.4

Example 7 Acetic Acid Using Nafion/Silica Composite SAC 13 as Catalyst

[0111] Reaction C S Y Example Catalyst time [h] [%] [%] [%] 8 Nafion SAC13 32 55.2 4 51.8

[0112] Analysis of methyl acetoxystearate

[0113] Characterization of compound II. Methyl 9(10)-acetoxystearate¹H-NMR 0.81 ppm tr 3H (chain end methyl group), 1.19- 1.6 ppm aplurality of broad peaks (chain methylene groups), 1.97 ppm s 3H (CH₃group acetoxy group), 2.27 ppm tr 2H (CH₂ group next to the methyl estergroup), 3.60 ppm s 3H (O—CH₃ group), 4.78 ppm q 1H (ester-substituted CHgroup) ¹³C-NMR 14.15 ppm (chain end CH₃ group), 21.34 ppm (CH₃ groupacetoxy group), peaks of 22.73 to 34.17 ppm (chain methylene groups),74.53 ppm (ester-substituted CH group), 174.13 ppm (CH₂CO₂CH), 179.97ppm (CH₃C—CO₂—CH) IR 1164 cm⁻¹ v_(as) C—O—C, 1283 cm⁻¹ v_(as) C—O—C,1361 cm⁻¹ δs CH₃/CH₃—CO₂—, 1435 cm⁻¹ δs CH₂/—CH₂—CO—C, 1462 cm⁻¹ δasCH₃, 1481 cm⁻¹ δs CH₂, 1745, 1726 cm⁻¹ C═O, 2926, 2856 cm⁻¹ v_(s.as)CH₂, CH₃ MS m/z: 356 (M⁺.), 355, 313, 295, 281, 263, 245, 187, 155, 109,95, 81, 67, 55

[0114] Boiling point: 170-182° C./5·10⁻² mbar

Example 8

[0115] 30 g of Nafion SAC 13 were dried under high vacuum at atemperature of 100° C. over a period of four hours, then introduced intoa 2 l one-neck flask and admixed with 100 g of a fatty acid methyl estermixture having a methyl oleate content of 66%. 570 g of pivalic acidwere added with stirring using a magnetic stirrer bar, then the flaskwas introduced into an oil bath heated to 120° C. Over a period of 15 h,the mixture was stirred with cooling by a reflux condenser. After theend of the reaction, a sample was taken and analyzed by gaschromatography using a 60 m Chrompack SE-54 column. A conversion ofmethyl oleate of 45% at a selectivity for the addition product of 96%was determined.

[0116] The reaction proceeds according to equation (4):

[0117] The catalyst was then filtered off and freed of reaction mixtureresidues by washing with acetone. The acetone was then distilled off atatmospheric pressure and the remaining residue united with the reactionmixture. If the catalyst should be deactivated after such a reaction, itis regenerated by treatment with hydrochloric acid.

[0118] The reaction mixture was then fractionated under high vacuum.Pivalic acid came over at 82° C./25 torr, methyl oleate and theremaining reactant components at 133° C./1·10⁻¹ mbar and methyl9-(10)-[2,2-dimethylpropionyloxy]stearate at from 170 to 174° C./1·10⁻¹mbar. 30 g of product mixture having a methyl9-(10)-[dimethylpropionyloxy]stearate content of 70% are obtained.

[0119] Characterization of compound III: methyl9-(10)-[2,2′-dimethylpropionyloxy]stearate ¹H-NMR 0.8 ppm tr 3H (chainend methyl group), 1.13 ppm s 9H (tert-butyl group), 1.19- 1.6 ppm aplurality of broad peaks (chain methylene groups), 2.12 ppm tr 2H (CH₂group next to the methyl ester group), 3.59 ppm s 3H (O—CH₃ group), 4.78ppm q 1H (ester- substituted CH group) ¹³C-NMR 14.12 ppm (chain end CH₃group), 27.25 ppm (tert-butyl group), 7 peaks of 22.66 to 34.14 ppm(chain methylene groups), 38.84 ppm {(CH₃)₃C}, 51.44 ppm (O—CH₃ group),73.81 ppm (ester-substituted CH group), 174.35 ppm (—CH₂CO₂CH₃), 178.27ppm {(CH₃)₃C—CO₂—CH} IR 1164 cm⁻¹ v_(as) C—O—C, 1283 cm⁻¹ v_(as) C—O—C—,1435 cm⁻¹ δs CH₂/—CH₂—CO—C, 1462 cm⁻¹ δas CH₃, 1480 cm⁻¹ δs CH₂, 1742,1726 cm⁻¹ C═O, 2950, 2926, 2856 cm⁻¹ v_(s.as) CH₂, CH₃ MS m/z: 399(M⁺.), 313, 297, 265, 247, 220, 111, 97, 95, 83, 69, 57, 55

[0120] Boiling point: 170-174° C./1·10⁻¹ mbar Elemental analysis:C_(found): 72.4% C_(calculated): 72.3% H_(found): 12.0% H_(calculated):11.6%

Examples 9 and 10

[0121] Examples 9 and 10 illustrate a comparison of the catalysts NafionSAC 13 (A) and Amberlyst 15 (B) in the addition of pivalic acid to thedouble bond of methyl oleate. The reaction parameters were: catalystvelocity 4 mmol/g of catalyst, molar excess of pivalic acid compared tomethyl oleate=25, temperature 120° C., reaction time 8 hours, batchreaction under atmospheric pressure; catalysts used without precedingdrying. Methyl oleate Selectivity Yield of conversion for compoundcompound Example Catalyst [%] III [%] III [%] 9 A 32 98 31 10 B 22 50 11

Examples 11 to 13

[0122] Examples 11 to 13 show a comparison of different Y-zeolites asheterogeneous catalysts in the addition of pivalic acid to the doublebond of methyl oleate. The reaction parameters were: catalyst velocity 4mmol/g of catalyst, molar excess of pivalic acid compared to methyloleate=25, temperature 120° C., reaction time 48 h, batch reaction underatmospheric pressure, catalysts used after preceding calcining at 550°C. for 12 hours Manufacturer and SiO₂/Al₂O₃ Catalyst number referencemodulus 7 Valor CBV-730 22 9 CBV-780SDUS 28 32 CBU-780 24

[0123] Selectivity Yield of Methyl oleate for compound compound ExampleCatalyst conversion III [%] III [%] 11 7 45.6 91.0 41.5 12 9 33.5 92.230.9 13 32 34.3 93 31.9

Examples 14 and 15

[0124] Example 14 shows the reproducibility of the results with theY-zeolite which corresponds to catalyst 7. Example 15 showed that theY-zeolite after calcining can be used repeatedly without, as is observedfor catalyst 32, losing activity. In both examples, the addition ofpivalic acid to the double bond of methyl oleate was carried out as inexamples 11 to 13. The reaction parameters were catalyst velocity 4mmol/g of catalyst, molar excess of pivalic acid compared to methyloleate=25, temperature 120° C., reaction time: 48 h, batch reactionunder atmospheric pressure; catalysts used after preceding calcining at550° C. for 12 hours. Methyl oleate Selectivity Yield of conversion forcompound compound Example Catalyst [%] III [%] III [%] 14 7 46.7 91.942.9 15 32 40.4 90.8 36.7

Examples 16 to 18

[0125] Examples 16 to 18 illustrate the effect of a higher degree ofbranching of the added carboxylic acid on conversion and selectivity.The starting materials were methyl oleate, Nafion SAC 13 catalyst, amolar excess of carboxylic acid compared to methyl oleate=50 (pivalicacid=25), temperature 120° C., reaction time 8 h, batch reaction underatmospheric pressure; catalyst used without preceding drying.Selectivity Yield of Methyl oleate for stearic stearic Carboxylicconversion acid adduct acid adduct Example acid used [%] [%] [%] 16Formic acid 83 77 64 17 Acetic acid 47 83 39 18 Pivalic acid 32 98 31

Examples 19 and 20

[0126] Examples 19 and 20 show the scale-up of the addition of pivalicacid to the double bond of methyl oleate. The catalyst was Nafion SAC13, and the reaction parameters were: catalyst velocity 4 mmol/g ofcatalyst, molar excess of pivalic acid compared to methyl oleate=25,temperature 120° C., batch reaction under atmospheric pressure;catalysts used without preceding drying. Quantity of Re- ConversionSelectivity Yield of methyl action of methyl of compound compound Ex-oleate used time oleate III III ample [g] [h] [%] [%] [%] 19 1 8 29 8826 20 100 15 32 98 31

Examples 21 to 25

[0127] Examples 21 to 25 illustrate the behavior of the reaction systemwhen Nafion SAC 13 is pretreated, reused and regenerated in the additionof pivalic acid to the double bond of methyl oleate. The reactionconditions were: catalyst velocity 4 mmol/g of catalyst, molar excess ofpivalic acid compared to methyl oleate=25, temperature 120° C., batchreaction under atmospheric pressure, reaction time 15 h. ConversionSelectivity Yield of of methyl of compound compound Ex- Catalyst oleateIII III ample treatment [%] [%] [%] 21 Untreated 29 88 26 22 Dried underhigh 45 96 44 vacuum at 20° C. for 24 h 23 2nd use, washed with 36 89 32acetone and dried 24 3rd use, washed with 33 97 32 acetone and dried 25Used, washed with 41 91 38 acetone and regenerated with HCl, dried

Example 26

[0128] In a further experiment, 3-benzyloxy-2,2-dimethylonic propionicacid was used as the acid component.

3-Benzyloxy-2,2-dimethylpropionic acid

[0129]

[0130] The spectroscopic data of the compound have already been reportedfurther back in the text. Nafion SAC 13 was used as catalyst foracyloxylating methyl oleate. The following reaction conditions wereselected: catalyst velocity 4 mmol/g of catalyst, molar excess ofpivalic acid compared to methyl oleate=25, temperature 120° C., batchreaction under atmospheric pressure, reaction time 24 h. ConversionSelectivity Yield of of methyl for target target Catalyst oleatecompound compound Example treatment [%] [%] [%] 26 Dried under high 26.536.3 9.6 vacuum at 20° C. for 24 h

Example 27

[0131] Example 27 illustrates the properties of the methylformyloxystearate and methyl [2,2-dimethylpropionyloxy]-stearate estersprepared according to examples 1 and 4 compared to pure methyl oleate(base raw material). Methyl Methyl formyl- Methyl [2,2-dimethyl- oleateoxystearate propionyloxy] stearate KV (40° C.) 4.5 12.0 13.1 [mm²/s] KV(100° C.) 1.7 3.1 3.4 [mm²/s] VI 178 120 139 ROBOT¹⁾ [min] 10 165 27Pour point [° C.] −18 −18 −9 Boiling point 133/ 160-174/ 170-174/ [° C.]10⁻¹ mbar 10⁻¹ mbar 10⁻¹ mbar Density (15° C.) 933.65 902.73 [kg/m³]

Further Examples

[0132] Further useful branched carboxylic acids for addition to thedouble bonds of natural fatty acids and natural fatty acid derivativesinclude, for example, the following carboxylic acids whose spectroscopicproperties have already been reported individually in the description:

1. A composition of matter, in particular a lubricant or a pressuretransfer medium, comprising fatty acids and/or fatty acid derivatives inwhich at least one double bond is acyloxylated.
 2. The composition ofmatter, in particular a lubricant or a pressure transfer medium, asclaimed in claim 1, wherein the double bond is acyloxylated bycarboxylic acid radicals.
 3. The composition of matter, in particular alubricant or a pressure transfer medium, as claimed in claim 1 or 2,wherein at least one double bond of the fatty acids and/or fatty acidderivatives and/or mixtures thereof is acyloxylated by unbranchedcarboxylic acids of the general chemical formula IV:

where R₈ is H or a linear alkyl radical having from 2 to 16 carbonatoms, preferably from 2 to 4 carbon atoms, or an aromatic radical whosearomatic core may be substituted by alkyl groups and/or halogens such asF.
 4. The composition of matter, in particular a lubricant or a pressuretransfer medium, as claimed in claim 1 or 2, which falls under thegeneral formula I

where R₁₄ is a carboxylic acid radical R—COOH where R is an alkyl,alkenyl, dienyl or polyenyl radical having from 2 to 20 carbon atoms andfrom 0 to 4 double bonds, preferably having from 3 to 11 carbon atomsand from 0 to 2 double bonds, for example, n-carboxyheptyl,n-carboxyundecyl, n-carboxy-4-heptenyl or esters thereof withmonoalcohols, diols or polyols, such as methanol, ethanol, glycerol,pentaerythritol or trimethylolpropane; R₁₅ is an alkyl, alkenyl, dienylor polyenyl radical having from 2 to 20 carbon atoms and from 0 to 4double bonds, preferably from 3 to 14 carbon atoms and from 0 to 3double bonds, in particular from 3 to 10 carbon atoms and from 0 to 2double bonds, for example, n-hexyl, n-octyl, 2-octenyl or2,5-octadienyl; and R₁₆ is H or R₁₆ is an alkyl radical having from 1 to10 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl or cyclohexyl; an arylradical having alkyl and other substituents on the aromatic ring, forexample phenyl, methylphenyl, ethylphenyl, mesityl, cumyl,p-nitrophenylxylyl, hydroxyphenyl or naphthyl; an aralkyl radical, forexample benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl,cumylmethyl or mesitylmethyl; an alkyloxy radical having from 1 to 10carbon atoms and phosphorus or sulfur as a further heteroatom, forexample methoxy, ethoxy, propyloxy, butyloxy, 2-ethylbutyloxy,3-thiabutyloxy, 3-phosphabutyloxy; an aralkyloxy radical having alkyland heteroatom-containing substituents on the aromatic ring, for examplebenzyloxy, 1-phenylethyloxy, (2-methyl)phenylmethoxy, p-sulfobenzyloxyor p-nitrobenzyloxy; and where R₁₇=R₁₈=R₁₆, except when R₁₆ is H, whereR₁₆, R₁₇ and R₁₈ may be identical or different and, when R₁₆ is H, R₁₇and R₁₈ may be identical or different.
 5. The composition of matter, inparticular a lubricant or a pressure transfer medium, as claimed in anyof claims 1 to 4, wherein the fatty acid and/or fatty acid derivativecontained therein is oleic acid, linoleic acid, linolenic acid,palmitoleic acid, eicosenoic acid, erucic acid or mixtures thereof ormethyl oleate, methyl linoleate, methyl linolenate, methyl palmitoleate,glycerol trioleate, glycerol trilinolate, glycerol trilinoleate,trimethylolpropane trioleate, trimethylolpropane trilinolate,trimethylolpropane trilinoleate, pentaerythritol tetraoleate,pentaerythritol tetralinolate, pentaerythritol tetralinoleate ormixtures thereof or renewable raw
 6. The composition of matter, inparticular a lubricant or a pressure transfer medium, as claimed inclaim 4 or 5, wherein the double bond is acyloxylated by radicals ofneocarboxylic acids of the general chemical formula V:

where R₉, R₁₀, R₁₂ and/or R₁₃ are identical or different and arehydrogen, straight-chain or branched alkyl, alkenyl or alkynyl radicalshaving up to 18 carbon atoms, cycloalkyl or cycloalkenyl radicals havingfrom 5 to 8 carbon atoms, aryl, aralkyl or alkenylaryl radicals havingfrom 6 to 16 carbon atoms or heterocyclic radicals, where each of the R₉and R₁₀ and/or R₁₂ and R₁₃ radical pairs together with the carbon atomto which they are bonded may form a cycloalkane, cycloalkene or aheterocycle having from 5 to 7 ring members, and R₉, R₁₀, R₁₂ and R₁₃may additionally carry substituents, in particular those which are inertunder the reaction conditions, and R₁₁ is hydrogen or a straight-chainor branched alkyl radical.
 7. The composition of matter, in particular alubricant or a pressure transfer medium, as claimed in claim 6, whereinneocarboxylic acids falling under the general chemical formula V includethose where R₉, R₁₀, R₁₂ and R₁₃ are identical or different and arehydrogen, straight-chain or branched alkyl radicals having from 1 to 12,in particular from 1 to 6 carbon atoms, alkenyl or alkynyl radicalshaving from 2 to 12, in particular from 2 to 6 carbon atoms, or whereR₉, R₁₀, R₁₂ and R₁₃ are cycloalkyl or cycloalkenyl radicals having 5 or6 carbon atoms, or are aryl, alkylaryl, aralkyl or alkenylaryl radicalshaving from 6 to 12 carbon atoms or heterocyclic radicals which containone or more nitrogen and/or oxygen and/or sulfur atoms, and where R₁₁ ishydrogen or a straight-chain or branched alkyl radical having from 1 to12, in particular from 1 to 8, preferably from 1 to 4 carbon atoms, andis more preferably hydrogen.
 8. A process for preparing compositions ofmatter, in particular lubricants and pressure transfer media as claimedin any of claims 1 to 7 by acyloxylating at least one double bond offatty acids and/or fatty acid derivatives and/or mixtures thereof, whichcomprises carrying out the acyloxylation using carboxylic acids orcarboxylic anhydrides or carbonyl halides.
 9. The process as claimed inclaim 8, wherein the acyloxylation is carried out without a catalyst orin the presence of homogeneous or heterogeneous acid catalysts.
 10. Theprocess as claimed in claim 8 or 9, wherein the heterogeneous acidcatalyst used is a zeolite, solid phosphoric acid, a phosphate ofaluminum, boron, iron, strontium, cerium or zirconium, an oxide such asAl₂O₃, SiO₂, B₂O₃, Fe₂O₃, ZrO₂, SnO₂ and GeO₂ or an organic ionexchanger such as Amberlyst or Nafion and the homogeneous acid catalystused is H₂SO₄, methylsulfonic acid, H₃PO₄ or derivatives thereof, H₃BO₃,HNO₃, HCl, HF, HF—BF₃, AlCl₃, FeCl₃, SnCl₂, AlBr₃ or FeBr₃.
 11. Theprocess as claimed in any of claims 8 to 10, wherein the acyloxylationis carried out in liquid phase at temperatures in the range from 0 to400° C., under a pressure in the range from 1000 to 10,000 hPa and overa duration in the range of from 1 min to 12 days.
 12. The use ofcompositions of matter as claimed in any of claims 1 to 7 as lubricantsand pressure transfer media in pure form or as lubricant additives, asfunctional liquids in hydraulic oils or for tribosystems. 13.Neocarboxylic acids for preparing compositions of matter, in particularlubricants or pressure transfer media as claimed in any of claims 4 to 7selected from the group consisting of: 3-propyloxy-2,2-dimethylpropionicacid, 3-butyloxy-2,2-dimethylpropionic acid,3-isobutyloxy-2,2-dimethylpropionic acid,3-(2-ethylbutyloxy)-2,2-dimethylpropionic acid,3-benzyloxy-2,2-dimethylpropionic acid and3-(2-methylphenyloxy)-2,2-dimethylpropionic acid.